Manufacture of sulfur dyestuffs



Patented Nov. 19, 1929 HERMANN PLAUSOILOF HAMBURG, GERMANY, ASSIGNOR TO DISPEROID SYNDICATE,

. .LTD., OF LONDON, ENGLAND I MANUFACTURE OF SULFUR DYESTUFFS This invention relates to the manufacture of dark or black dyes containing sulfur.

One of the objects of the invention is the production of a dye direct from a carbonaceous material by the action of sulfur in conjunction with an alkali metal compound having an alkaline reaction. Other objects of the invention are the production of black brownish-black or brownish-yellow sulfur dyes directly from such raw materials as bitumens,=-pitches, soots, peat and the like and also earthy coals, lignite, cannel coal, pitch coal, anthracite and lampblack. The raw materials are subjected to a sulfurizing process by heating with sulfur and an alkali metal compound having an alkaline reaction such as sodium sulfid, sodium hydrate, sodium carbonate, or the like. According to one feature of the invention the carbonaceous nomenor that powdered materials of the kind referred tosuch as lignite or pitch coal by melting in an admixture with sulfur alone or with polysulfides giving a colloidal product like a sulfur dye and the process is illustrated by the following examples.

Ewample 1 T No Drawing. Application filed June 28, 1924, Serial No: 722,954, and in Germany July 2, 1923.

example at 200 C. there is formed a dyestuff which gives cotton a light brown tone. A dark brown-black is obtained if the temperature rises to 300. If a final temperature of 300 to 310 is employed there results on cooling a dry crumbly black powder which gives with water a colloidal dye bath with which cotton can be directly dyed black. The purification of the dye stufi is possible by the known methods of precipitating with acids or salts etc. but is not however, necessary. In the dyeing process Turkey red oil can be added by which means a warm brown orblack is produced.

The process can also be carried out under pressure in the presence of water according to the following example.

Example 2 1000 parts of sodium sulfid, 400 parts of sulfur and 500 parts of lignite are heated with vigorous stirring in an autoclave preferably while passing in superheated steam.

Example 3 Example 4 A black dye for the oil and printing trade can be obtained without the application of sodium sulfid by the following method. 500 parts of powdered lignite are stirred up with 500 parts of concentrated sulfuric acid. To this are added 750 parts of sulfur, and the mass then heated in the absence of air to to There is formed thereby a dry mass with the evolution of sulfur dioxid which when cold can be well powdered. By washing with boiling, weakly alkaline water, a good black dye is obtained which can be used as a substitute for the finest lamp black. If sodium sulfid is added to the substances, the mass can be converted to the soluble state by further heating at 300.- Instead of lignite 100 reacted upon b all kinds of cannel coal or similar Example 5 Production of color lakes. 1000 parts of sodium sulfid, 400 parts of sulfur and 500 parts of powdered lignite are treated according to Example 1. The aqueous solution of this dye stuff is mixed with 5000 parts of ordinary clay. By heating, the clay is precipitated according to the known method, treated with a 1% solution of bichromate or other metal salts or tannin, neutralized, washed and dried. There is obtained in this way an extremely finely powdered black dye which finds application in the textile industry or as a ,filling material for plastic masses, for staining, or the manufacture of boot polish. Instead of clay, other neutral earths such as ochre can be used. They must, however, always be present in a highly dispersed state or must be converted by the known method into the colloidal form for their application.

Example 6' 100' parts of crude bitumen from lignite are 240 parts of: sodium sulfid and 100 parts 0 sulfur according to Example 1. After heating for 3 to 5 hours at 200to 250 the mass is allowed to cool and dried, preferably undervacuum. A dark brown dye stuff results. 'If the bitumen is treated with concentrated or preferably with fuming sulfuric acid and afterwards the sulfonated product treated by the before described polysulfid melt, a deep black dye stuff is obtained. Useful results may be obtained by'pretreata ment with sulfur chlorid. If the bitumen is treated with a sulfuric acid saltpeter mixture, a brown-black tone is produced, whereas by previous treatment with chlorine a dark green results. Instead of bitumen, lignite or pitch coal'of all kinds can be treated by a sulfonation, nitration or chlorination process. The relative amount of resulting product'and the operating temperature can be altered according to the shade desired. For the purpose of producing difi'erent tints a small addition of compounds of an organic or inorganic nature can be made, for example, the phenols and their derivatives, aniline or its derivatives,

or homologues, benzidin'e, chlor-di-nitrobenzene, naphthalene, indo-phenol, urea, etc.

.Eaample' 7 may be employed. If the amount of sulfur and sodium sulfid in the melt and the time of heating be increased, a substantially black dye is produced. Similar products are also obtained if an addition of copper salts, or chromium compounds to a small amount was made to the melt.

The proportional amounts of sodium sulfid,

sulfur and coal can be altered according to the desired dyeing effect. The process can naturally be carried out according to the previous examples.

Ewample 8 1250 parts of sodium sulfid, 500 parts of Example 9 500 parts of lamp black, 1250 parts of sodium sulfid, 500 parts of sulfur are treated as in Examples 7 or 8, at a temperature of 300 to 400 C. or at most 450.

black colloid. The pure lamp black may be mixed with 3 to 10 parts or more of the bituminous extraction production of anthraclte,

A Subv stantially bitumen-free lamp black gives a' pitch coal or such like charcoal or pitch prodnets, and if these mixtures are acted upon by the polysulfid melt, a fast dyeresults.

In the preceding examples sodium sulfide has always been employed. Now it has been found that the sodium sulfide is not absolute- 1y necessary, but can be replaced by other alkalis, e. g., caustic alkali or alkali metal carbonate. This way of proceeding is not oh- I vious since sodium hydrate and especially sodium carbonate only react very slowly with sulfur and it was not known that coal is al-v tered by such a mixture. Experiment has shown that a sulfur melt by the action of sodium hydroxide or carbonate furnishes directly, a 'dyestuif. If a good result is required, it is advantageous to increase the sulfur content above that indicated in the previous examples.

Example 10 I 800 grams NaOH, 800 grams sulfur and 400 grams lignite are melted together and heated with stirring to between 300350. After being allowed to cool the mass is pow dered as finely as possible in a ball mill or alkali metal hydroxides can be. employed.

The same result is reached if instead" of lignite, cannel coal, turbanite or other bituminous coal is employed. A good black dye is obtained which easily dyes cotton and artificial silk:

4 of sulfur dyes.

Example 11 500 grams of finely pulverized English anthracite, 820 grams sulfur and 1000 grams of caustic soda are subjected to a melt as in Example 1 at a temperature of 300-350". After cooling and powdering, a dark brown dyestufi is obtained. When heated for a longer time to 350-47 0 the product takes on a dark black tone. The solubility in this case is further improved by further addition of alkali metal sulfide. The dyeing can be carried out according to Example 10 with or without addition of fixing materials or of dye improvers.

Example 12 1000 parts of caustic soda, 850 parts of sulfur and 500 parts of charcoal or pitch coal, produced at the lowest possible temperature, are formed into a melt and then slowly heated from 350-450? The mass can, after cooling, be ground to a fine owder. which on the addition of sodium sul d can be completely brought into solution. In a similar manner difierent lamp blacks can also be used for the production of dyestufls.

E wample 13 106 parts of calcined soda, parts of sulfur and 40 to 50 parts of lignite are heated under continual stirring to 300350. The reaction goes slowly and almost imperceptibly and finally a yellow vapour is evolved and the usual deflagration takes place as is frequently to be observed in the production A deep black powder is formed whose solution glves cotton or artificial silk a warm dark brown tone. By longer melting at the above mentioned temperature or by the addition of small amounts of inorganic or organic compounds as toning agents to the melt or to the dyebath, a black dye shade can be obtained. Instead of calcined soda, crystallized sodium carbonate in a corresponding amount can be used. Other carbonates are also applicable; the best re sult is given, however, by sodium carbonate.

All the other examples may be carried out with alkali metal carbonate instead of hydroxide, if mineral coals are used as starting materials. Inthe using of crystalline soda it has shown itself to .be profitable to carry out the melt in an autoclave, for instance, under pressure; there is obtained in this wa a particularly hdmogeneous end product. aturally the process can take place with reflux condensation of the water of crystallization.

It has also been found that it is possible to simplify the production of sulfur dyestufi's from mineral coal for the like carbonaceous material if the sulfur-alkali, melt is not applied directl to the mixed constituents, but

coal and sul ur are first heated together and then directly, after or before cooling and powdering, the product of the melt is subj ected to the action of a further melting with the addition of the necessary amount of caustic alkali or alkali metal sulfid. The dyestufl obtained in this way gives a considerably deeper black, and the action of the alkali melt is more complete and simple as the frothing and similar undesirable phenomena are eliminated from the process.

Example 14 '400 grams of lignite or the like bituminous coal is heated with 800 grams sulfur to 120-. 4

150, preferably in the absence of air for 10 3 to 30 minutes. After this time the melt can be cooled and then pulverized or directly treated further by heating with 800-1000 grams caustic soda, preferably in absence of air to BOO-400 C. until a homogeneous melt results.

There is obtained a very good dye of deep black tone. Instead of caustic alkali a suit-' able amount of alkali metal sulfid such as 'sodium sulfid, can be taken. In the latter vantageous in the melting with sulfur to add compounds of copper, iron, zinc, nickel, cobalt, tin or chromium, or the metals themselves in the powder form in amounts of 1-5% as thereby the dyes possess an especially full tone. 'organic compounds suitable for altering the In similar manner smallamounts of It has also been found that dyes which.

produce a deep black on diiferent materials can be obtained, if the impure Eonstituents are removed from the crude coal before the 'polysulfid meltin the dye synthesis. With this object the coal is treated in a pressure autoclave-or in a colloid mill or similarly acting apparatus with alkali and water and freed cotton or on artificial by filtering or settlin from the valueless materials. The suspen ed material is then precipitated with a weak aseous acid such as carbon dioxid, sulfur dloxid, or by a dilute acid such as hydrochloric, sulfuric, nitric acid orthe like. There is obtained in this manner as starting material for the dye manufacture a purified and more or less opened up preparation. 4

This product is dried and can be used directly for the production of sulfur dyestuffs according to the processes of the previous examples. In certain cases it can be subjected with advantage, even in the moist state to a process of sulfonation, oxidation, chlorination, nitration, azotization (azotierungs) or reduction according to' the tint desired, or even to several of the above substitution proc esses in any suitable order. The product obtained by extracting coal such as crude bitumen, pitch bitumen and the like with organic solvents, can be treated in similar manner.

The characteristic feature of this part of the process consists in the fact that the starting materials for the manufacture of the dyestufl, obtained by the above described methods of purification or extraction are always produced without the application of dry distillation. 'Only these g ve, in fact the desired deep black dyes as resulting products while those obtained throughthe distillation of car'- bonaceous materials are of no value as they almost always suffer deep seated changes.

If the product obtained from coal by the above method is subjected to the polysulfid melt, a deep black dyestufi' is obtained which is absorbed by cotton much better than the substance produced by the direct process from coal.

E wample 15 i 100 parts of lignite- (ash content 16% are mixed with 100 parts of alkali and 500 parts of water and heated in an autoclave for 1 to 2 hours. After dilution with 2000 parts of water it is allowed to settle and purified from.

Y the insoluble part by filtration or by slight described in the previous examples. Black' dyes are obtained by the chlorination or sulfonation or the like, according to the manner Ewample -1 6 If the bitumen has been obtained according to a known process by extraction with hydrocarbons, the residue is worked as in Examples 15 or 16. The product obtained by this opening u process is added to the bitumen obtained rom the extraction process before the further treatment by the known process by extraction with hydrocarbons, the residue is worked as in Example 15. The product obtained by this opening up process is added to the bitumen obtained from the extraction process before the further treatment by the melting process or by a solution process. Y

The working of the product obtained from Examples 15 or 16 can always be carried out in two .ways. Either it can be subjected directly to a polysulfid melt or first by'a known method to sulfonation, chlorination, nitration, or other conversion processes customary in the production of organic dyes, such as nitrification (azotierung) condensation and the like, and these products can then be converted by a melt with alkali and sulfur to the dyestuff. The result in both cases is a dyestufi which produces on the material a black-green tone, whereby if necessary, the chlorination or nitration or the like which has'been accomshade of the pure product, which can also be influenced in this way if desired.

For the improvement of the tint of the dye taken up, small amounts of. organic compounds can be employed which give d es in. the polysulfid melt which are suitable fbr altering as desired, the shade of the final product towards green-black or blue-black. Naturallythe choice of these will be governed by all previously gathered experience on the action of the order of substitution on the shade. Such compounds, for example, as para-nitroso-phenol and para-amido-phenol paradihydroxybenzene, and moreover dinitraniline, dinitrophenol and the like are suitable. For obtaining bluer tints, naphthalene derivatives, for example, substituted in the peri-position are employed with success. Halogenindophenols alter the shade towards the green, indophenols chlorinated in the nucleus towards the green-blue and unchlorinated indophenols towards the pure blue.

In the appended claims, by semi carbonized carbonaceous material I mean material which by a naturalprocess or by an artificial heat treatment, has been" partly decomposed to yield aresidiieconsisting of carbon, more or less loosely chemically bound'with other sub stances, and which'may be a solid or liquid. or semiliquid mass. H

The term ,coal substance comprises all coals, lignite's and solid or'semiliquid'carbonaceous products derived therefrom.

I declare that-what I claim is 1. Process for the production of a dye in which semicarbonized carbonaceous material is heated with sulfur and afterwards heated with an inorganic substance of an alkaline nature.

2. Process for the production of a dye in which semicarbonized carbonaceous material after incomplete combustion is heated with sulfur-and afterwards heated with an? inorganic substance of an alkaline nature 3. Process forthe production of a dye in which a coal substance is heated with sulfur and afterwards heated with an inorganic substance of an alkaline nature.

4. Process for the production of a dye in which lignite is heated with sulfur and aftermelt dissolved in water and the dyestuff precipitated with clay.

- 13. Process for the production of a dyestiiif in which semicarbonized carbonaceous In witness whereof, I have hereunto signed my name.

I-IERMANN' PLAUSON.

wards heated with an inorganic substance of.

an alkaline nature.

5. Process for the production. of a dye in which a semicarbonized carbonaceous material is heated with sulfur, with an inorganic A 6. Process for the production of a dye in 'whichsemicarbonized carbonaceous material is pre-treated with a chemical reagent containing active chlorine and is then heated with sulfur and with an inorganic substance of an alkaline nature.

7. Process for the production of a dye in which a semicarbonized carbonaceous material is pre-treated with chlorine and then is heated with sulfur and with an inorganic substance of an alkaline nature.

8. Process for the production of a vdye in which a semicarbonized carbonaceous material is pre-treated with chlorine and then subjected to the action of a polysulfid melt.

-9. Process for the production of a dye in which a semicarbonized carbonaceous material is heated with sulfur, and with an inorganic substance of an alkaline'nature and a heavy metal salt.

10. Process for the production of a dye in which a semicarbonized carbonaceousmaterial is heated with sulphur and afterwards vwith sodium sulfid.

11. Process for the production of a, dye in 1 ganic substance of an alkaline nature, the 

